Blocking layers for leakage current reduction in DRAM devices

ABSTRACT

A method for forming a DRAM MIM capacitor stack having low leakage current involves the use of a first electrode that serves as a template for promoting the high k phase of a subsequently deposited dielectric layer. The high k dielectric layer comprises a doped material that can be crystallized after a subsequent annealing treatment. An amorphous blocking is formed on the dielectric layer. The thickness of the blocking layer is chosen such that the blocking layer remains amorphous after a subsequent annealing treatment. A second electrode layer compatible with the blocking layer is formed on the blocking layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a Divisional Application of U.S. patent application Ser. No. 13/290,795, filed on Nov. 7, 2011, which is herein incorporated by reference for all purposes.

This document relates to the subject matter of a joint research agreement between Intermolecular, Inc. and Elpida Memory, Inc.

FIELD OF THE INVENTION

The present invention generally relates to the field of dynamic random access memory (DRAM), and more particularly to dielectric material processing for improved DRAM performance.

BACKGROUND OF THE INVENTION

Dynamic Random Access Memory utilizes capacitors to store bits of information within an integrated circuit. A capacitor is formed by placing a dielectric material between two electrodes formed from conductive materials. A capacitor's ability to hold electrical charge (i.e., capacitance) is a function of the surface area of the capacitor plates A, the distance between the capacitor plates d (i.e. the physical thickness of the dielectric layer), and the relative dielectric constant or k-value of the dielectric material. The capacitance is given by:

$\begin{matrix} {C = {{\kappa ɛ}_{o}\frac{A}{d}}} & \left( {{Eqn}.\mspace{14mu} 1} \right) \end{matrix}$ where ∈_(o) represents the vacuum permittivity.

The dielectric constant is a measure of a material's polarizability. Therefore, the higher the dielectric constant of a material, the more charge the capacitor can hold. Therefore, if the k-value of the dielectric is increased, the area of the capacitor can be decreased and maintain the desired cell capacitance. Reducing the size of capacitors within the device is important for the miniaturization of integrated circuits. This allows the packing of millions (mega-bit (Mb)) or billions (giga-bit (Gb)) of memory cells into a single semiconductor device. The goal is to maintain a large cell capacitance (generally ˜10 to 25 fF) and a low leakage current (generally <10⁻⁷ A cm⁻²). The physical thickness of the dielectric layers in DRAM capacitors could not be reduced unlimitedly in order to avoid leakage current caused by tunneling mechanisms which exponentially increases as the thickness of the dielectric layer decreases.

Traditionally, SiO₂ has been used as the dielectric material and semiconducting materials (semiconductor-insulator-semiconductor [SIS] cell designs) have been used as the electrodes. The cell capacitance was maintained by increasing the area of the capacitor using very complex capacitor morphologies while also decreasing the thickness of the SiO₂ dielectric layer. Increases of the leakage current above the desired specifications have demanded the development of new capacitor geometries, new electrode materials, and new dielectric materials. Cell designs have migrated to metal-insulator-semiconductor (MIS) and now to metal-insulator-metal (MIM) cell designs for higher performance.

One class of high k dielectric materials possessing the characteristics required for implementation in advanced DRAM capacitors are high k metal oxide materials. Examples of suitable dielectric materials comprise Al₂O₃, BaSrTiO_(x) (BST), HfO₂, HfSiO_(x), Nb₂O₅, PbZrTiO_(x) (PZT), SiO₂, a bilayer of SiO₂ and Si_(x)N_(y), SiON, SrTiO₃ (STO), Ta₂O₅, TiO₂, ZrO₂, etc. TiO₂ and ZrO₂ are two specific examples of metal oxide dielectric materials which display significant promise in terms of serving as a high k dielectric material for implementation in DRAM capacitors.

Typically, DRAM devices at technology nodes of 80 nm and below use MIM capacitors wherein the electrode materials are metals. These electrode materials generally have higher conductivities than the semiconductor electrode materials, higher work functions, exhibit improved stability over the semiconductor electrode materials, and exhibit reduced depletion effects. The electrode materials must have high conductivity to ensure fast device speeds. Representative examples of electrode materials for MIM capacitors are metals, conductive metal oxides, conductive metal silicides, conductive metal nitrides (i.e. TiN), or combinations thereof. MIM capacitors in these DRAM applications utilize insulating materials having a dielectric constant, or k-value, significantly higher than that of SiO₂ (k=3.9). For DRAM capacitors, the goal is to utilize dielectric materials with k values greater than about 40. Such materials are generally classified as high k materials. Representative examples of high k materials for MIM capacitors are non-conducting metal oxides, non-conducting metal nitrides, non-conducting metal silicates or combinations thereof. These dielectrics may also include additional dopant materials.

A figure of merit in DRAM technology is the electrical performance of the dielectric material as compared to SiO₂ known as the Equivalent Oxide Thickness (EOT). A high k material's EOT is calculated using a normalized measure of silicon dioxide (SiO₂ k=3.9) as a reference, given by:

$\begin{matrix} {{EOT} = {\frac{3.9}{\kappa} \cdot d}} & \left( {{Eqn}.\mspace{14mu} 2} \right) \end{matrix}$ where d represents the physical thickness of the capacitor dielectric.

As DRAM technologies scale below the 40 nm technology node, manufacturers must reduce the EOT of the high k dielectric films in MIM capacitors in order to increase charge storage capacity. The goal is to utilize dielectric materials that exhibit an EOT of less than about 0.8 nm while maintaining a physical thickness of about 5-20 nm.

Generally, as the dielectric constant of a material increases, the band gap of the material decreases. For example. The rutile phase of TiO₂ has a k-value of about 80 and a band gap of about 3.0 eV while ZrO₂ in the tetragonal phase has a k-value of about 43 and a band gap of about 5.8 eV. The low band gap may lead to high leakage current in the device. As a result, without the utilization of countervailing measures, capacitor stacks implementing high k dielectric materials may experience large leakage currents. High work function electrodes (e.g., electrodes having a work function of greater than 5.0 eV) may be utilized in order to counter the effects of implementing a reduced band gap high k dielectric layer within the DRAM capacitor. Metals, such as platinum, gold, ruthenium, and ruthenium oxide are examples of high work function electrode materials suitable for inhibiting device leakage in a DRAM capacitor having a high k dielectric layer. The noble metal systems, however, are prohibitively expensive when employed in a mass production context. Moreover, electrodes fabricated from noble metals often suffer from poor manufacturing qualities, such as surface roughness, poor adhesion, and form a contamination risk in the fab.

Conductive metal oxides, conductive metal silicides, conductive metal nitrides, or combinations thereof comprise other classes of materials that may be suitable as DRAM capacitor electrodes. Generally, transition metals and their conductive binary compounds form good candidates as electrode materials. The transition metals exist in several oxidation states. Therefore, a wide variety of compounds are possible. Different compounds may have different crystal structures, electrical properties, etc. It is important to utilize the proper compound for the desired application.

In one example, molybdenum has several binary oxides of which MoO₂ and MoO₃ are two examples. These two oxides of molybdenum have different properties. MoO₂ has shown great promise as an electrode material in DRAM capacitors. MoO₂ has a distorted rutile crystal structure and serves as an acceptable template to promote the deposition of the rutile-phase of TiO₂ as discussed above. MoO₂ also has a high work function (can be >5.0 eV depending on process history) which helps to minimize the leakage current of the DRAM device. However, oxygen-rich phases (MoO_(2+x)) degrade the performance of the MoO₂ electrode because they do not promote the deposition of the rutile-phase of TiO₂ and have higher resistivity than MoO₂. For example, MoO₃ (the most oxygen-rich phase) has an orthorhombic crystal structure and is a dielectric.

Generally, a deposited thin film may be amorphous, crystalline, or a mixture thereof. Furthermore, several different crystalline phases may exist. Therefore, processes (both deposition and post-treatment) must be developed to maximize the formation of crystalline MoO₂ and to minimize the presence of MoO_(2+x) phases. Deposition processes and post-treatment processes in a reducing atmosphere have been developed that allow crystalline MoO₂ to be used as the first electrode (i.e. bottom electrode) in DRAM MIM capacitors with TiO₂ or doped-TiO₂ high k dielectric materials. Examples of the post-treatment process are further described in U.S. application Ser. No. 13/084,666 filed on Apr. 12, 2011, entitled “METHOD FOR FABRICATING A DRAM CAPACITOR” which is incorporated herein by reference. However, these DRAM MIM capacitors have continued to use noble metal (i.e. Ru) materials for the second electrode (i.e. top electrode).

After the formation of the second electrode, the capacitor stack is then subjected to a post metallization anneal (PMA) treatment. The PMA treatment serves to crystallize the second electrode and to anneal defects in the dielectric and interface states that are formed at the dielectric/second electrode interface during the deposition. Also, if there is no post dielectric anneal (PDA) treatment done before metallization, the PMA treatment can serve to crystallize the dielectric layer to improve the k value and fill oxygen vacancies. Examples of the PDA and PMA treatments are further described in U.S. application Ser. No. 13/159,842 filed on Jun. 14, 2011, entitled “METHOD OF PROCESSING MIM CAPACITORS TO REDUCE LEAKAGE CURRENT” and is incorporated herein by reference. As discussed above, MoO₂ is sensitive to oxidation to form oxygen-rich compounds that negatively impacts its performance as an electrode material. The reducing atmosphere anneal processes discussed previously with respect to the use of crystalline MoO₂ as a first electrode are not an option at this stage of the device manufacture because they would degrade the performance of the dielectric layer through the formation of oxygen vacancies. TiO₂ high k dielectric materials are especially sensitive to processing conditions and increases in the leakage current are observed, likely due to the formation of oxygen vacancies.

As discussed previously, the rutile phase of TiO₂ is an attractive candidate high k dielectric material with a k-value in excess of about 80 depending on processing conditions. The high k-value should allow the formation of MIM capacitor stacks with low EOT values within the physical thickness constraints of advanced DRAM technologies. The use of crystalline MoO₂ would be attractive as a first electrode since it would serve as a good template to promote the formation of the rutile phase of TiO₂. Ideally, the crystalline MoO₂ would be used as the second electrode as well to form a symmetric MIM stack. However, currently Ru is used for the second electrode due to integration issues surrounding the use of MoO₂ as the second electrode. As discussed previously, both MoO₂ and TiO₂ are very sensitive to the environment used during the various annealing steps. The oxidation of MoO₂ to MoO_(2+x) and the loss of oxygen in TiO₂ to form oxygen vacancies both contribute to the higher leakage current observed in MIM stacks using these materials. As an example, TiO₂ MIM capacitors can have leakage currents in the range of about 8×10⁻⁶ A/cm² at an EOT of about 0.38 nm to about 1.0×10⁻⁷ A/cm² at an EOT of about 0.50 nm.

Leakage current in capacitor dielectric materials can be due to Schottky emission, Frenkel-Poole defects (e.g. oxygen vacancies (V_(ox)) or grain boundaries), or Fowler-Nordheim tunneling. Schottky emission, also called thermionic emission, is a common mechanism and is the thermally activated flow of charge over an energy barrier whereby the effective barrier height of a MIM capacitor controls leakage current. The nominal barrier height is a function of the difference between the work function of the electrode and the electron affinity of the dielectric. The electron affinity of a dielectric is closely related to the conduction band offset of the dielectric. The Schottky emission behavior of a dielectric layer is generally determined by the properties of the dielectric/electrode interface. Frenkel-Poole emission allows the conduction of charges through a dielectric layer through the interaction with defect sites such as vacancies, grain boundaries, and the like. As such, the Frenkel-Poole emission behavior of a dielectric layer is generally determined by the dielectric layer's bulk properties. Fowler-Nordheim emission allows the conduction of charges through a dielectric layer through direct tunneling without any intermediary interaction with e.g. defects. As such, the Fowler-Nordheim emission behavior of a dielectric layer is generally determined by the physical thickness of the dielectric layer. This leakage current is a primary driving force in the adoption of high-k dielectric materials. The use of high-k materials allows the physical thickness of the dielectric layer to be as thick as possible while maintaining the required capacitance (see Eqn 1 above).

As discussed previously, materials with a high k value generally have a small band gap. The small band gap leads to high leakage current through the Schottky emission mechanism due to the small barrier height. The leakage current may be reduced through the use of a blocking layer that has a higher band gap. Therefore, there is a need to develop methods for forming capacitor stacks that incorporate blocking layers to reduce the leakage current.

SUMMARY OF THE DISCLOSURE

In some embodiments of the present invention, a crystalline MoO₂ first electrode is used to promote the formation of the rutile phase of a TiO₂ dielectric layer that is subsequently formed. The MoO₂ first electrode may be annealed to increase the crystallinity and to reduce unwanted MoO_(2+x) phases that may be present. The TiO₂ dielectric layer may be doped to reduce the leakage current. An amorphous blocking layer is formed on top of the TiO₂ dielectric layer. The amorphous blocking layer is a dielectric material with a k value between about 10 and about 30 and the band gap of the blocking layer is greater than about 4.8 eV. Advantageously, the barrier height between the amorphous blocking layer and the second electrode is greater than about 1.2 eV. Examples of suitable blocking layer materials comprise Er₂O₃, Ga₂O₃, Gd₂O₃, La₂O₃, ZrO₂, or doped versions of the same. The amorphous blocking layer reduces the leakage current of the capacitor stack. The first electrode layer, TiO₂ dielectric layer, and blocking layer may be annealed to increase the crystallinity of the TiO₂ dielectric layer and to reduce the concentration of oxygen vacancies that may be present in the TiO₂ dielectric layer. A second electrode is formed on top of the amorphous blocking layer. The second electrode is compatible with the amorphous blocking layer and is compatible with current DRAM manufacturing process flows.

BRIEF DESCRIPTION OF THE DRAWINGS

To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. The drawings are not to scale and the relative dimensions of various elements in the drawings are depicted schematically and not necessarily to scale.

The techniques of the present invention can readily be understood by considering the following detailed description in conjunction with the accompanying drawings, in which:

FIG. 1 illustrates a flow chart illustrating a method for fabricating a DRAM capacitor stack in accordance with some embodiments of the present invention.

FIG. 2 illustrates a simplified cross-sectional view of a DRAM capacitor stack fabricated in accordance with some embodiments of the present invention.

FIG. 3 presents data illustrating the leakage current as a function of EOT for a number of dielectric films and blocking layers according to some embodiments herein.

FIG. 4 presents data illustrating the leakage current as a function of physical thickness for a number of dielectric films and blocking layers according to some embodiments herein.

FIG. 5 presents data illustrating the leakage current as a function of EOT for a number of dielectric films and blocking layers according to some embodiments herein.

FIG. 6 illustrates a simplified cross-sectional view of a DRAM memory cell fabricated in accordance with some embodiments of the present invention.

DETAILED DESCRIPTION

A detailed description of one or more embodiments is provided below along with accompanying figures. The detailed description is provided in connection with such embodiments, but is not limited to any particular example. The scope is limited only by the claims and numerous alternatives, modifications, and equivalents are encompassed. Numerous specific details are set forth in the following description in order to provide a thorough understanding. These details are provided for the purpose of example and the described techniques may be practiced according to the claims without some or all of these specific details. For the purpose of clarity, technical material that is known in the technical fields related to the embodiments has not been described in detail to avoid unnecessarily obscuring the description.

FIG. 1 describes a method, 100, for fabricating a DRAM capacitor stack. The initial step, 102, comprises forming a first electrode layer on a substrate. Examples of suitable electrode materials comprise metals, metal alloys, conductive metal oxides, conductive metal silicides, conductive metal nitrides, or combinations thereof. A particularly interesting class of materials is the conductive metal oxides. Optionally, the first electrode layer can then be subjected to an annealing process (not shown). The next step, 104, comprises forming a crystalline, doped dielectric material on the first electrode layer. The next step, 106, comprises forming an amorphous blocking layer on the dielectric layer. Optionally, the first electrode layer, the dielectric layer, and the blocking layer can then be subjected to an annealing process (not shown). The next step, 108, comprises forming a second electrode layer on the blocking layer to complete the formation of the capacitor stack. Typically, the capacitor stack is then subjected to a PMA anneal treatment.

Those skilled in the art will appreciate that each of the first electrode layer, the dielectric layer, the blocking layer, and the second electrode layer used in the DRAM MIM capacitor may be formed using any common formation technique such as atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PE-ALD), atomic vapor deposition (AVD), ultraviolet assisted atomic layer deposition (UV-ALD), chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), or physical vapor deposition (PVD). Generally, because of the complex morphology of the DRAM capacitor structure, ALD, PE-ALD, AVD, or CVD are preferred methods of formation. However, any of these techniques are suitable for forming each of the various layers discussed below. Those skilled in the art will appreciate that the teachings described below are not limited by the technology used for the deposition process.

In FIGS. 2 and 6 below, a capacitor stack is illustrated using a simple planar structure. Those skilled in the art will appreciate that the description and teachings to follow can be readily applied to any simple or complex capacitor morphology. The drawings are for illustrative purposes only and do not limit the application of the present invention.

FIG. 2 illustrates a simple capacitor stack, 200, consistent with a DRAM MIM capacitor stack according to some embodiments of the present invention comprising a crystalline metal oxide first electrode layer, a crystalline, doped high k dielectric layer, an amorphous blocking layer, and a second electrode layer. First electrode layer, 202, is formed on substrate, 201. Generally, the substrate has already received several processing steps in the manufacture of a full DRAM device. First electrode layer, 202, comprises one of metals, metal alloys, conductive metal oxides, conductive metal nitrides, conductive metal silicides, or combinations thereof, etc. For this example, first electrode layer, 202, comprises a conductive metal oxide that may serve to promote the rutile phase of TiO₂. Examples of such conductive metal oxides include the conductive compounds of molybdenum oxide, tungsten oxide, ruthenium oxide, iron oxide, iridium oxide, chromium oxide, manganese oxide, tin oxide, cobalt oxide, or nickel oxide. A specific electrode material of interest is the crystalline MoO₂ compound of molybdenum dioxide.

Optionally, first electrode layer, 202, can be annealed to crystallize the material. In the case of crystalline MoO₂, it is advantageous to anneal the first electrode layer in a reducing atmosphere such as Ar, N₂, or forming gas to prevent the formation of oxygen-rich compounds as discussed previously.

In one example of a DRAM MIM capacitor stack comprising crystalline metal oxide electrode layers and a doped high k dielectric layer, a first electrode comprising between about 5 nm and about 10 nm of molybdenum oxide is formed on a substrate. The molybdenum oxide electrode material is formed at a process temperature between about 125 C and 400 C using an ALD process technology. Optionally, the substrate with the first electrode is then annealed in a reducing atmosphere comprising between about 1% and about 20% H₂ in N₂ and advantageously between about 5% and about 10% H₂ in N₂ between 400 and 520 C for between about 1 millisecond and about 60 minutes as discussed previously.

In the next step, dielectric layer, 204, would then be formed on the annealed first electrode layer, 202. A wide variety of dielectric materials have been targeted for use in DRAM capacitors. Examples of suitable dielectric materials comprise Al₂O₃, BaSrTiO_(x) (BST), HfO₂, HfSiO_(x), Nb₂O₅, PbZrTiO_(x) (PZT), SiO₂, a bilayer of SiO₂ and Si_(x)N_(y), SiON, SrTiO₃ (STO), Ta₂O₅, TiO₂, ZrO₂, or doped versions of the same. These dielectric materials may be formed as a single layer or may be formed as a hybrid or nanolaminate structure. A specific dielectric material of interest is TiO₂ doped with one of Al, Ce, Co, Er, Ga, Gd, Ge, Hf, In, La, Lu, Mg, Mn, Nd, Pr, Sc, Si, Sn, Sr, Y, Zr, or combinations thereof. A specific dielectric material of interest is TiO₂ doped with Al₂O₃ to between about 5 atomic % and about 15 atomic % Al (Al/(Al+Ti) atomic %).

In a specific example, the, doped dielectric layer comprises between about 6 nm to about 10 nm of TiO₂ wherein at least 30% of the TiO₂ is present in the rutile phase. Generally, the TiO₂ dielectric layer may either be a single film or may comprise a nanolaminate. Advantageously, the TiO₂ material is doped with Al at a concentration between about 5 atomic % and about 15 atomic % Al. The TiO₂ dielectric layer is formed at a process temperature between about 200 C and 350 C using an ALD process technology.

In the next step, amorphous blocking layer, 206, would then be formed on the crystalline, doped dielectric layer, 204. A wide variety of dielectric materials have been targeted for use as blocking layers in DRAM capacitors. Examples of suitable blocking layer materials comprise Er₂O₃, Ga₂O₃, Gd₂O₃, La₂O₃, ZrO₂, or doped versions of the same. These materials have a band gap that is greater than about 4.8 eV. Advantageously, the barrier height between the amorphous blocking layer and the second electrode is greater than about 1.2 eV. These dielectric materials may be formed as a single layer or may be formed as a hybrid or nanolaminate structure. Suitable dopants for use with the blocking layer materials comprise Al, Co, Ge, Hf, Mg, Si, Sn, Sr, Ti, Y, or combinations thereof. The dopant concentration is selected such that the blocking layer remains amorphous (<about 30% crystalline as determined by x-ray diffraction (XRD)) after subsequent annealing treatments. The blocking layer needs to be thick enough that it forms a continuous layer. Therefore, the minimum thickness is about 0.5 nm. Additionally, the blocking layer should be thin enough that it remains amorphous after subsequent annealing treatments. Therefore, the maximum thickness is about 2.0 nm. Advantageously, the thickness of the blocking layer is in the range from about 0.7 nm to about 1.5 nm. The thickness of the blocking layer is typically less than or equal to about 25% of the total dielectric thickness of the DRAM MIM capacitor (i.e. the total thickness of the combination of the crystalline, doped high k dielectric layer and the amorphous, doped high k second dielectric layer).

The substrate with the first electrode layer, a doped high k dielectric layer, and an amorphous blocking layer is then annealed in an oxidizing atmosphere comprising between about 0% O₂ to about 100% O₂ in N₂ and advantageously between about 0% O₂ to about 20% O₂ in N₂ at temperatures between about 400 C to about 600 C for between about 1 millisecond to about 60 minutes. The doped high k dielectric layer will be crystalline (>about 30% crystalline as determined by XRD) after the anneal.

In the next step, the second electrode layer, 208, is formed on blocking layer, 206 to complete the formation of the capacitor stack. The second electrode layer may be a one of, metals, metal alloys, conductive metal oxides, conductive metal nitrides, conductive metal silicides, or combinations thereof, etc. Examples of suitable materials for the second electrode layer comprise Co, CoN, Ir, MoN, MoO₂, Ni, NiN, NiO, Pt, Pd, Ru, RuO₂, TiN, VN, WN, or combinations thereof. The capacitor stack may receive a PMA treatment as discussed previously.

DRAM MIM capacitors with the configuration illustrated in FIG. 2 will exhibit low leakage current due to the current blocking properties of the amorphous blocking layer. The higher band gap (i.e. >about 4.8 eV) of the blocking layer reduces the leakage current due to the Schottky emission mechanism. The barrier height between the amorphous blocking layer and the second electrode (i.e. >about 1.2 eV) also reduces the leakage current due to the Schottky emission mechanism. Additionally, the DRAM MIM capacitor will exhibit low EOT values due to the high k value of the crystalline, doped high k dielectric layer. A further benefit of the DRAM MIM capacitor stack illustrated in FIG. 2 is that it is easy to integrate into existing DRAM manufacturing process flows. The use, treatment, materials compatibility, reliability, etc. of metal nitride second electrode materials are well established. Therefore, the DRAM MIM capacitor stack illustrated in FIG. 2 represents an opportunity to integrate the benefits of the MoO₂ first electrode and the high k properties of doped TiO₂ into the DRAM MIM manufacturing process without having to adapt to the use of new material as a second electrode.

The benefits of some embodiments of the present invention are illustrated in the data presented in FIG. 3. A first group of simple capacitor stacks were formed comprising a MoO₂ first electrode, an Al-doped TiO₂ dielectric layer, and a Pt second electrode. These samples are denoted TA-A Pt TEC in the legend and illustrated by the black circles in FIG. 3. A second group of simple capacitor stacks were formed comprising a MoO₂ first electrode, an Al-doped TiO₂ dielectric layer, a doped amorphous ZrO₂ blocking layer, and a Pt second electrode. These samples are denoted TA-Z Pt TEC in the legend and illustrated by the gray triangles in FIG. 3. As illustrated in FIG. 3, The TA-Z Pt TEC samples exhibited lower leakage current than the TA-A Pt TEC samples at a given EOT thickness. Additionally, the TA-Z Pt TEC samples exhibited a lower EOT for an equivalent level of leakage current.

The benefits of some embodiments of the present invention are illustrated in the data presented in FIG. 4. A first group of simple capacitor stacks were formed comprising a MoO₂ first electrode, an Al-doped TiO₂ dielectric layer, and a Pt second electrode. These samples are denoted TA+Pt TEC in the legend and illustrated by the black circles in FIG. 4. A second group of simple capacitor stacks were formed comprising a MoO₂ first electrode, an Al-doped TiO₂ dielectric layer, a doped amorphous ZrO₂ blocking layer, and a Pt second electrode. These samples are denoted TA-Z+Pt TEC in the legend and illustrated by the gray triangles in FIG. 4. As illustrated in FIG. 4, The TA-Z+Pt TEC samples exhibited lower leakage current than the TA+Pt TEC samples at a given physical thickness.

A number of materials may be suitable as blocking layers. They should have k values between about 10 and about 30 and will therefore have band gaps that are higher than TiO₂ (preferably >about 4.8 eV). Table 1 lists a number of potential candidates, their k values, and their band gap compared to TiO₂.

TABLE 1 Material K Value Band Gap (eV) TiO₂ 80 3.5 Er₂O₃ 13 7.8 Ga₂O₃ 10 4.8 Gd₂O₃ 16 5.3 La₂O₃ 30 6.0 ZrO₂ 43 5.8

The benefits of some embodiments of the present invention are illustrated in the data presented in FIG. 5. A first group of simple capacitor stacks were formed comprising a MoO₂ first electrode, an Al-doped TiO₂ dielectric layer, and a Pt second electrode. These samples are denoted TA-Al in the legend and illustrated by the black diamonds in FIG. 5. A second group of simple capacitor stacks were formed comprising a MoO₂ first electrode, an Al-doped TiO₂ dielectric layer, a doped amorphous ZrO₂ blocking layer, and a Pt second electrode. These samples are denoted TA-Zr in the legend and illustrated by the black triangles in FIG. 5. A third group of simple capacitor stacks were formed comprising a MoO₂ first electrode, an Al-doped TiO₂ dielectric layer, a doped amorphous La₂O₃ blocking layer, and a Pt second electrode. These samples are denoted TA-La in the legend and illustrated by the black circles in FIG. 5. A fourth group of simple capacitor stacks were formed comprising a MoO₂ first electrode, an Al-doped TiO₂ dielectric layer, a doped amorphous Er₂O₃ blocking layer, and a Pt second electrode. These samples are denoted TA-Er in the legend and illustrated by the black squares in FIG. 5. As illustrated in FIG. 5, The TA-Zr and TA-La samples exhibited lower leakage current than the TA-Al samples at a given physical thickness. The TA-Er samples exhibited higher leakage indicating that this material may not be a suitable candidate as a blocking layer. As an example, highlighting the data at about 0.55 nm EOT (since future DRAM technology nodes will require smaller values of EOT), the TA-La samples had a leakage current of about 1.7×10⁻⁷ A/cm², the TA-Zr samples had a leakage current of about 2.9×10⁻⁷ A/cm², compared to the TA-Al samples (the control group) which had a leakage current of about 1.6×10⁻⁶ A/cm².

An example of a specific application of some embodiments of the present invention is in the fabrication of capacitors used in the memory cells in DRAM devices. DRAM memory cells effectively use a capacitor to store charge for a period of time, with the charge being electronically “read” to determine whether a logical “one” or “zero” has been stored in the associated cell. Conventionally, a cell transistor is used to access the cell. The cell transistor is turned “on” in order to store data on each associated capacitor and is otherwise turned “off” to isolate the capacitor and preserve its charge. More complex DRAM cell structures exist, but this basic DRAM structure will be used for illustrating the application of this disclosure to capacitor manufacturing and to DRAM manufacturing. FIG. 6 is used to illustrate one DRAM cell, 620, manufactured using a bilayer dielectric structure as discussed previously. The cell, 620, is illustrated schematically to include two principle components, a cell capacitor, 600, and a cell transistor, 602. The cell transistor is usually constituted by a MOS transistor having a gate, 616, source, 612, and drain, 614. The gate is usually connected to a word line and one of the source or drain is connected to a bit line. The cell capacitor has a lower or storage electrode and an upper or plate electrode. The storage electrode is connected to the other of the source or drain and the plate electrode is connected to a reference potential conductor. The cell transistor is, when selected, turned “on” by an active level of the word line to read or write data from or into the cell capacitor via the bit line.

As was described previously, the cell capacitor, 600, comprises a first electrode layer, 604, formed on substrate, 601. The first electrode layer, 604, is connected to the source or drain of the cell transistor, 602. For illustrative purposes, the first electrode has been connected to the source, 612, in this example. As discussed previously, first electrode layer, 604, may be subjected to an anneal in a reducing atmosphere before the formation of the dielectric layer if the first electrode layer is a conductive metal oxide such as MoO₂. Crystalline, doped high k dielectric layer, 606, is formed on top of the first electrode layer. If the crystalline, doped high k dielectric layer is TiO₂, then the dielectric layer will be lightly or non-doped so that the rutile phase of TiO₂ can be formed on the bottom electrode. Typical dopants for TiO₂ comprise Al, Ce, Co, Er, Ga, Gd, Ge, Hf, In, La, Lu, Mg, Mn, Nd, Pr, Sc, Si, Sn, Sr, Y, Zr, or combinations thereof. Amorphous blocking layer, 608, is formed on top of the dielectric layer. As discussed previously, the second dielectric layer may be doped. The blocking layer may be highly doped so that it will remain amorphous (<30% crystalline) after subsequent anneal steps. Examples of suitable blocking layer materials comprise Er₂O₃, Ga₂O₃, Gd₂O₃, La₂O₃, ZrO₂, or doped versions of the same. The blocking layer should have a band gap greater than about 4.8 eV. Advantageously, the barrier height between the amorphous blocking layer and the second electrode is greater than about 1.2 eV. Typically, the first electrode layer, the high k dielectric layer, and the blocking layer are then subjected to a PDA treatment. The second electrode layer, 610, is then formed on top of the blocking layer. This completes the formation of the capacitor stack. Typically, the capacitor stack is then subjected to a PMA treatment.

Although the foregoing examples have been described in some detail for purposes of clarity of understanding, the invention is not limited to the details provided. There are many alternative ways of implementing the invention. The disclosed examples are illustrative and not restrictive. 

What is claimed:
 1. A method for forming a capacitor stack, the method comprising: forming a MoO₂ first electrode layer on a substrate; forming a TiO₂ dielectric layer on the MoO₂first electrode layer, wherein the MoO₂ first electrode operates as a template promoting formation of a rutile phase of the TiO₂ dielectric layer, wherein the TiO₂ dielectric layer comprises a first dopant, and wherein the TiO₂ dielectric layer is more than about 30% crystalline after a subsequent annealing treatment; forming a La₂O₃ blocking layer on the TiO₂ dielectric layer, wherein the La₂O₃ blocking layer comprises a second dopant, and wherein the La₂O₃ blocking layer is amorphous after the subsequent annealing treatment; and forming a second electrode layer on the La₂O₃ blocking layer.
 2. The method of claim 1 further comprising annealing the MoO₂ first electrode layer before the forming of the TiO₂ dielectric layer.
 3. The method of claim 1 further comprising annealing the MoO₂ first electrode layer, the TiO₂ dielectric layer, and the La₂O₃ blocking layer after the forming of the La₂O₃ blocking layer and before the forming of the second electrode layer.
 4. The method of claim 1 wherein the MoO₂ first electrode layer, the TiO₂ dielectric layer, the La₂O₃ blocking layer and the second electrode layer are subjected to an annealing treatment after the formation of the second electrode layer.
 5. The method of claim 1 wherein the first dopant comprises one of Al, Ce, Co, Er, Ga, Gd, Ge, Hf, In, La, Lu, Mg, Mn, Nd, Pr, Sc, Si, Sn, Sr, Y, Zr, or combinations thereof.
 6. The method of claim 1 wherein the La₂O₃ blocking layer is thinner than the TiO₂ dielectric layer.
 7. The method of claim 1 wherein the thickness of the La₂O₃ blocking layer is less than about 2.0 nm.
 8. The method of claim 1 wherein the thickness of the La₂O₃ blocking layer is between about 0.7 nm and about 1.5 nm.
 9. The method of claim 1 wherein the thickness of the La₂O₃ blocking layer is less or equal to about 25% of the total dielectric thickness of the capacitor stack.
 10. The method of claim 1 wherein a barrier height between the La₂O₃ blocking layer and the second electrode layer is greater than about 1.2 eV.
 11. The method of claim 1, wherein the first dopant comprises Al₂O₃ and wherein the concentration of the first dopant in the TiO₂ dielectric layer is between about 5 atomic % and about 15 atomic %.
 12. The method of claim 1, wherein the second dopant comprises Al, Co, Ge, Hf, Mg, Si, Sn, Sr, Ti, Y, or combinations thereof.
 13. The method of claim 1, wherein the La₂O₃ blocking layer has a thickness of at least about 0.5 nm.
 14. The method of claim 1, wherein the second electrode layer comprises one of Co, CoN, Ir, MoN, MoO2, Ni, NiN, NiO, Pt, Pd, Ru, RuO2, TiN, VN, WN, or combinations thereof.
 15. The method of claim 1, wherein the La₂O₃ blocking layer is a nanolaminate structure.
 16. The method of claim 1, wherein La2O3 blocking layer further comprises one of Er₂O₃, Ga₂O₃, Gd₂O₃, or ZrO₂.
 17. The method of claim 1 wherein the second electrode layer comprises one of Co, CoN, Ir, MoN, MoO₂, Ni, NiN, NiO, Pt, Pd, Ru, RuO₂, TiN, VN, WN, or combinations thereof.
 18. The method of claim 17 wherein the MoO₂ first electrode layer is subjected to an annealing treatment before the formation of the TiO₂ dielectric layer.
 19. The method of claim 17 wherein the MoO₂ first electrode layer, the TiO₂ dielectric material, and the La₂O₃ blocking are subjected to an annealing treatment after the formation of the La₂O₃ blocking layer and before the formation of the second electrode layer.
 20. The method of claim 17 wherein the MoO₂ first electrode layer, the TiO₂ dielectric layer, the La₂O₃ blocking layer, and the second electrode layer are subjected to an annealing treatment after the formation of the second electrode layer. 